Method of and means for waving hair



March 22, 1938. IRL. EVANS ET AL 2,111,553

r v METHOD OF AND MEANS FOR WAQING HAIR Filed May 25, 1934 looooooooo #41?) WW MW; 6 Mun aw ATTORNEY Patented Mar. 22, 1938 METHOD OF MEANS FOR WAVING HAIR Ralph L. Evans, New York, and Everett G. McDonough, Mount Vernon, N. Y., assignors to Zotos Corporation, New York, N. Y., a corporation of New York Application May 28, 1934, Serial No. 727,154

36 Claims. '(Cl. 13246.2).

Our invention relates generally to the art of chemical heaters and in its more specific aspect to the art of producing a so-called permanent wave in living human hair by subjecting the hair to heat produced by exothermic reaction of a chemical mixture in proximity thereto.

Our invention presents many advantages in the composition of the chemicals or chemical mixtures used in the method of producing a permanent wave wherein the heat is generated by exothermic means.

We have been able to prepare compositions which are not sensitive to atmospheric influences. In mixtures heretofore used, atmospheric moisture and/or atmospheric carbon dioxide are readily absorbed and by thus decreasing the amount of heat available render the containing device useless after a short time. It is true that this difllculty may be overcome by mechanical means 50 such as the use of moisture-impermeable wrappings and/or sealing the finished pads within a metal container, but these expedients add to the production costs and are liable to failures from incomplete closure.

35 The heat generating ingredients heretofore used upon being wetted with water would swell as the reaction progressed. This swelling could be controlled by additions of proper materials but serious difficulties were still present in practical use. For instance, the removal of the pads from the confining container in the so-called croqulgnole method frequently required the use of considerable force. Also, in the spiral method there was danger of bursting the overlapping parchment by the swelling chemical within the pad. Resulting spilled powder could make an annoying mess or a bursting device accompanied by escaping steam could result in a burn to the person whose hair is being waved. These disadvantages are overcome in our invention, without the necessity of adding another material, by the use of substances whose reactions inherently do not give rise to swelling or bursting.

Moreover, ingredients heretofore used produce a reaction when wet with water whose total exothermic heat might be barely sufficient to impart a wave to a properly treated strand of hair. To obtain more heat it would be necessary to increase proportionally the amounts (volumes and weights) of ingredicntsused. This makes the pad bulky and unwieldy for practical use and increases the weight and enhances the objection-- able swelling referred to in the preceding paravs p By our invention we are able to vary the total heat generated within very wide limits without unduly increasing the total weight. A simple change in proportions of ingredients is here utilized to effect the desired change.

Production diilicultiesiarise from the use of ingredients heretofore employed. The most commonly used material is quick-lime and the chemical properties of this material are well known to be easily altered during its production; variation in the source of limestone or the method of burning gives limes of entirely difierent heat generating activities. The handling of such sensitive materials necessitates utmost care because of the atmospheric influences above referred to. Continuous chemical control during manufacture and handling by checking and re-checking is necessary for uniform performance. These difficulties are obviated by our invention.

Basically there are available three general types of reaction which produce exothermic heat (1) neutralization (2) hydration (3) oxidation and reduction. Of these the oxidation-reduction type, to which this invention relates, presents advantages in the permanent waving of hair nolt2 possessed by the other two types of exotherm reactions.

In an oxidation-reduction reaction it is necessary for a transfer of electrons to take place; the substance or ion or radical being oxidized loses one or more electrons whereas the substance or ion or radical being reduced gains one or more electrons.

In nearly all classes of oxidation-reduction reactions in contact with water we have found that it is particularly necessary to control the hydrogen ion concentration in order to get the desired rate of transfer of electrons. In other words, the speed of the reaction is usually a function of the hydrogen ion concentration.

We have also found that the speed of the reaction at the optimum hydrogen ion concentration can be influenced :by the addition of substances known as catalysts either acting in a single capacity or preferably performing a double function, i. e.,'one, to assist in the ready acceptance of the electron by the substance to be reduced and, two, to assist the ready release of the electron from the substance to be oxidized.

Where the substances are pro-mixed in the dry state and water is later added to start the reaction, we have found that particle size will greatly influence the rate of heat evolution. The rate of solution is directly related to size of the particle being dissolved. Also if the oxidation-reduction system is heterogeneous the finer the paror nonmetals as sulfur, phosphorus, etc.

ticles of the substance in the solid state the faster will be the rate of reaction.

In the use of an oxidation-reduction reaction in the confinement of a small pack, we have found that it is frequently desirable not only to carefully control the speed of reaction but also to have present an absorbent material so that there will be no leakage of the solution. To this end we may advantageously rely upon a watery paste to hold the liquid within the pack. The absorbent material also acts as a diluent and gives more even distribution of chemicals so that a steady and easily regulated reaction occurs.

By these various controls of the speed of the exothermic reaction we are able to effect the proper time-temperature relationship for imparting a permanent wave to hair.

We have found that .the type of oxidation-reduction reaction most easily adapted to be used in a small pack and possessing advantages most needed in this method of permanent waving is one which utilires a substance to be oxidized which under the proper conditions easily loses electrons and a substance to be. reduced which easily acquires electrons. Examples of the first are metals such as magnesium, zinc, aluminum, iron, etc., or inorganic ions such as sulfite ion or thiosulfate ion, or organic materials ranging from simple ones like formic or oxalic acid to the myriad of much more complex reducing agents,

amples of the second are (a) oxygen rich matecentration often increases the speed of electron transfer in-such a reaction mixture. Too high hydrogen ion concentration, however, may cause undesirable by-product reaction, as for instance, hydrogen formation or the formation of free halogen or halogen oxide in a system unsuitable for their presence, or the complete solution or destruction of the catalyst or the absorbent material. We have found that the proper hydrogen ion concentration can be obtained from various substances; especially useful are such acidic materials as (a) small amounts of strong acids or larger amounts of weak acids (b) acid salts such as bisulfates, acid phosphates, bitartrates, etc.; (0) salts of strong acids with weak bases e. g.- aluminum sulfate, magnesium chloride, zinc chloride, etc. (d) salts capable of forming acidic solutions, such as persulfates, pyrocompounds, etc.

In order to regulate the rate of the electron transfer at the optimum hydrogen ion concentration, we may add a substance which enters the reaction in such a way that it both assists in the removal of the electron by the substance to be oxidized and/or accelerates the acceptance of the electron by the substance to be reduced. For example, in reactions where the substance to lose electrons is a metal such as zinc or aluminum and the substance to gain an electron is an ion such as persulfate, permanganate or chlorate ion, and the hydrogen ion concentration is properly controlled by such a substance as sodium dihydrogen phosphate or sodium bisulphate, we have found that the addition of a substance such as an oxygen unsaturated metal oxide or salt, e. g.copper oxide, will act in such a manner as to accelerate the electron transfer. In this particular example cited copper oxide in contact with a solution of sufficient hydrogen ion concentration will react to form nascent metallic copper and copper ion; the nascent metallic copper functioning to assist the metal aluminum to lose electrons and the copper ion functioning to assist the chlorate ion in accepting electrons. While we prefer to employ electron materials of the character indicated, others also may be used, such as the heavy metals and their compounds.

We have further found that the most suitable absorbent materials to add to such a system are inert substances such as silica, clay, titanium oxide, barium sulphate, calcium sulphate, or in fact, any suitable composition which will not react with the other materials employed. These materials possess the added advantages among others of making premature reaction or explosion from the close frictional contact of oxidizing and reducing materials impossible, of being unaffected by atmospheric influences, of effecting even distribution of the chemicals and steadying the reaction and when made as a watery paste of holding the system within the pack; some have low apparent density by which property they give volume and permit easy dilution without materially increasing the weight.

Such a system as we have just described consisting of an oxidizable material, a reducible material, a hydrogen ion control material, an electron transfer material, and a water absorbent diluent material has the merits, among others, that it will not be affected by atmospheric in fiuence, it will not swell as the reaction proceeds, a wide variation in quantity of heat generated can be obtained without any objectionable increase in weight or volume, production and manufacture will be easy and stringent chemical control of production will be unnecessary. By way of exempliilcation but without limiting my invention or claim thereto, the following is given as typical example of a chemical mixture which will generate heat by electron transfer when wet with water:

Parts Aluminum 20- 60 Sodium persulfate 50- 500 Maleic acid 50- 150 Copper oxide 40- 100 Fullers earth 500-1000 In applying our chemical mixture to the waving of hair we may employ any suitable apparatus, such for instance, as that disclosed in the patent to Evans 1,927,544 and shown in the accompanying drawing, in which Fig. 1 is a side view of a hair waving apparatus in use;

Fig. 2 is a transverse cross-section taken on the line 2--2 of Fig. 1;

Fig. 3 is an inside plan view of a pad containing the chemical mixture, said pad being shown in unfolded condition.

Fig. 4 is an outside plan view of the same.

The tress to be waved is shown as wound on a mandrel I, mounted between two end members 2, 3, carried by two clamp members I, 5, hinged at 6, and held together at their free ends by a locking member I. The clamp members are provided with hair-engaging strips 8, 8, of suitable yielding insulating material and have uprising sides i0, I i operating to shield the scalp from heat and vapor. A pad I2 is interposed between the tress clamp and the scalp for a similar purpose.

The heating pad i5 is shown as comprising a backing portion IS, a ioldable portion I'I, an envelope [8 preferably of impervious material, as foil, which contains the exothermic material i9, the envelope being attached as by adhesive, or similar means, to the backing portion i8; and a sheet of absorbent material 20, as cotton fabric or blotting paper, secured in position to be folded acrossthe face of the exothermic material containing envelope 18. Inasmuch as our exothermic material does not deteriorate when exposed to air the exposed face of the envelope may conveniently be provided with perforations 2| in the manufacture of the pad, thus obviating the necessity of making these perforations at the time the pad is used, or if made at the time of manufacture, obviating the necessity of sealing such perforations by means of an additional impervious sheet, as has heretofore been the practice.

In practice,.the absorbent sheet is wetted by water or a suitable waving solution and folded across the perforated face of the envelope. The pad is then bent in U-shape and applied about the tress on the mandrel I, being held in place by the sides I0 and i i of the clamp.

It is evident that many changes may be made without departing from the spirit and scope of our invention.

We claim: i

1. Means for waving hair including a chemical mixture or chemical which when treated with a suitable substance generates heat by a chemical reaction involving a transfer of electrons from one of the substances to another of the substances, means for regulating the hydrogen ion concentration and means for accelerating electron acceptance, or of electron loss, or of both, to effect the proper time-temperature relationship for imparting a permanent wave to hair.

2. Means for waving hair including a chemical mixture or' chemical which when treated with a suitable substance generates heat by a chemical reaction of the oxidation-reduction type.

3. Means for waving hair including a chemical mixture or chemical which when treated with a suitable substance will generate heat sufficient to impart a permanent wave, the chemical reaction involving an electron transfer, the substance losing the electron being a metal.

4. Means for waving hair including a chemical mixture or chemical which when treated with a suitable substance will generate heat sufflcient to impart a permanent wave, the chemical reaction involving an electron transfer, the substance receiving the electron being the negative radical of an oxygen acid.

5. Means for waving hair including a chemical mixture 101' chemical which when treated with a suitable substance will generate sufiicient heat to permanentlywave the hair, said mixture being of a nature to permit the ,total heat output to'be varied bylchange in proportions of the ingredients without a significant change in volume or weight.

6. Means for waving hair including a chemical mixture or chemical which when treated with a suitable substance will generate sufficient heat to permanently wave the hair, the mixture being inherently of a nature to prevent the chemical reaction which generates heat from being accompanied by significant swelling.

7. Means for wavinghair including a chemical mixture or chemical which when treated with a suitable substance will generate sufficient heat to permanently wave the hair the activity of said mixture being unafiected by exposure to the atmosphere.

8. In heat generating means for waving hair in combination, a material which readily yields its electrons on oxidation, a material which readily absorbs electrons on reduction and an electron transfer material for facilitating the transfer of said electrons.

9. In a heat generating means for waving hair in combination, an oxidizable material, a reducible material, a hydrogen ion control material and an electron transfer material, for facilitating and regulating the oxidation and reduction of said former materials, respectively, and an absorbent diluent material.

10. In a heat generating means for waving hair in combination, an oxidizable material, a reducible material and a hydrogen ion control material for facilitating and regulating the oxidation and reduction of said former materials, respectively, to effect the proper time-temperature relationship for imparting a permanent wave to hair.

11. Means for waving hair including a chemical mixture or a chemical which when treated with a suitable substance will generate heat suiilcient to impart a permanent wave the chemical reaction involving an electron transfer, a metal such as aluminum or its equivalent constituting a source of electrons to be lost, a negative radical of oxygen acidconstituting an electron acceptor, an acidic substance constituting means for supplying the proper hydrogen ion control, a compound of: a heavy metal acting to assist in the loss of the Parts Aluminum 20- 60 Sodium persulfate 50- 500 Maleic acid 50- 150 Copper oxide g 40- Fullers earth L 500-1000 13. The method of waving hair including pre-- forming a tress of hair in the desired form, treat ing the hair with a waving lotion, generating heat by the reaction in a chemical mixture involving a gain of electrons by one of the components and a loss of electrons by another of the components, and applying the heat so generated to the hair.

14. The method of waving hair including preforming a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing a transfer of electrons from one component to another to efiect a loss of electrons by the one component and .a gain of electrons by another to generate heat, controlling the hydrogen ion concentration to regulate the rate of transfer of electrons and thereby heat generation, and applying the generated heat to the preformed hair.

15. The method of waving hair including preforming a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing a transfer of electrons from one substance to another to effect the generation of heat, regulating the hydrogen ion concentration, adding a substance or substances to accelerate the speed of electron acceptance, or of electron loss, or of both, to effect the proper time-temperature relationship for imparting a permanent wave to hair, and applying the generated heat tothe preformed hair.

16. The method of waving hair including preforming a tress of hair, providing a chemical mixture, causing a reaction between its components to effect the generation of heat, and adding a stabilizing material of a nature to prevent premature spontaneous or frictional reactions, and applying the generated heat to the preformed hair.

17. The method of waving hair including preforming a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing a transfer of electrons from one component to another to generate heat, the substance losing electrons being a metal, and applying the generated heat to the preformed hair.

18. The method of waving hair including preforrning a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing a transfer of electrons from one component to another to generate heat, the substance receiving the electron being the negative radical of an oxygen acid, and applying the generated heat to the preformed hair.

19. The method of waving hair including preforming a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing a transfer of electrons from one component to another to generate heat, adding an acidic material to regulate the rate of transfer whereby the proper hydrogen ion concentration is obtained, to effect the proper time-temperature relationship for imparting a permanent wave to hair, and applying the generated heat to the preformed hair.

20. The method of waving hair including preforming a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing a transfer of electrons reaction between its components, causing an oxidation-reduction reaction in the chemical mixture, and applying the generated heat to the preformed hair.

22. The method of waving hair including preforming a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing an electron transfer in the presence of a stabilizing material to prevent premature frictional or spontaneous reactions, and applying the generated heat to the preformed hair.

23. The method of waving hair including preforming a tress of hair, providing a chemical mixture, causing a reaction between its components to effect the generation of heat, varying the total heat output by changing the proportions of the ingredients without a significant change in total volume or weight, and applying the generated heat to. the preformed hair.

24. The method of waving hair including preforming a tress of hair, providing a chemical mixture, causing areaction between its components to effect the generation of heat, the nature of the chemical mixture inherently preventing the reaction from being accompanied by significant swelling, and applying the generated heat to the preformed hair.

25. The method of waving hair including preforming a. tress of hair, providing a chemical mixture whose heat generating power is unaffected by exposure to the atmosphere, causing a reaction between its components to effect the generation of heat, and applying the generated heat to the preformed hair.

26. The method of waving hair including preforming a tress of hair, providing a chemical mixture susceptible of electron transfer between its components, causing a transfer of electrons from one component to another to generate heat, employing a metal as a source of electrons to be lost, employing a negative radical of an oxygen acid as an electron acceptor, employing an acidic substance as a means for supplying the proper hydrogen ion control, employing a compound of a heavy metal to assist in the loss of the electrons, employing a substance of high absorbent properties such as minerals or treated minerals of high silica content, preferably inert, as a diluent and preventer of premature spontaneous reaction, and iapplying the generated heat to the preformed air.

27. The method of waving hair including preforming a tress of hair, providing a chemical or chemical mixture including- Parts Aluminum 20- 60 Sodium persulfate 50- 500 Maleic acid 50- 150 Copper oxide 40- 100 Fullers earth 500-1000 causing a reaction between said components to effect the generation of heat, and applying the generated heat to the preformed hair.

28. Means for waving hair including a chemical mixture or chemical which when treated with a suitable substance will generate heat sufficient to impart a permanent wave and means to prevent spontaneous or frictional reactions.

29. Means for waving hair including a chemical mixture or chemical which when treated with a suitable substance will generate heat by an electron transfer suflicient to impart a permanent wave and an absorbent material.

30. Means for waving hair including a chemical mixture or chemical which when treated with a suitable substance will generate heat suilficient to impart a permanent wave, the chemical reaction involving an electron transfer, and means including an acidic material for regulating the speed of transfer by furnishing the proper hydroen ion concentration, to effect the proper timetemperature relationship for imparting a permanent wave to hair.

31. Means for waving hair including a cherriical mixture or chemical which when treated with a suitable substance will generate heat sumcient to impart a permanent wave, the chemical least one substance for regulating the course of reaction involving an electron transfer and a the reaction in accordance with the desired time heavy metal compound for accelerating the elec temperature curve. tron transfer. '34. The combination as defined in claim 33, in

g 32. The method of waving hair including prewhich at least one of the regulating substances 15 forming a tress of hair, providing a chemical mix acts catalytically. ture susceptible of electron transfer between its 35. The combination as defined in claim 33, in components, causing a transfer of electrons from which the regulating substance is a metal salt one component to another in the presence 01' abhaving a catalytic action. m

1Q sorbent material to generate heat, and applying 36. The combination as defined in claim 33, in 10 the, generated heat to the preformed hair, which the regulating substance is a metal salt not 33. A heating mixture for the permanent wavsaturated with oxygen.

ing or hair containing an oxidizing agent, a reducing substance capable of reducing the oxi- RALPH L. EVANS.

ll dizlng agent with the generation of heat, and at EVERETT G. McDONOUGH. 15 

